1-alkoxy-1-aryloxy-2, 2, 3-trichloro-nu-butanes



Patented May 23, 1956 1-ALKOXY-1-ARYLOXY-2,2,3 -TRICHLORO N -BUTAN ESWalter D. Harris, Naugatuck, Coma, and Theodore W. Kerr, Kingston, R.I., assignors to United States Rubber Company, New York, N. Y., acorporation of New Jersey No Drawing. Application January 29, 1947,Serial No. 725,163

Claims. 1

This invention relates to improvements in insecticides. The terminsecticide is considered to include larvaecides, arachnicides, andinsect repellents or insectifuges, and is to be construed in accordancewith the Insecticide Act of 1910, section 6.

We have found that mixed aliphatic-aromatic acetals of butyl chloral areeifective insecticides. These are new chemicals which we have found tobe toxic to a wide variety of insects, including the greenhouse redspider mite and the Mexican bean beetle, which insects are notefiectively controlled by the known insecticide 2,2-bis (p-chiorophenyl)-1,1,l-trichlorethane (DDT). The mixed aliphatic-aromatic acetals ofbutyl chloral may be represented by the general formula:

in which X is an aliphatic radical and Y is an aromatic radical.Examples of the aliphatic radicals X are alkyl, cycloalkyl, haloalkyl,cyanoalkyl, alkoxyalkyl, hydroxyalkyl. Examples of the aromatic radicalsY are phenyl, naphthyl, halophenyl, nitrophenyl, alkylphenyl,alkoxyphenyl. The chemicals of the invention may also be classed asl-alkoxy-1-aryloxy-2,2,3-tri-,

chloro-n-butanes, where the alkoxy group may be considered a hydrocarbonalkyl ether linkage or a substituted alkyl ether linkage (e. g.haloalkyl, cyanoalkyl, alkoxyalkyl or hydroxyalkyl ether linkage) andthe aryloxy group may be considered a hydrocarbon aryl (e. g. phenyl ornaphthyl) ether linkage, or a substituted aryl ether linkage (e. g.haloaryl, nitroaryl, alkaryl or alkoxyaryl ether linkage).

The compounds of the present invention are readily prepared by refluxingthe selected phenolic compound with the selected aliphatic 1,2,23-tetrachloro-n-b-utyl ether. The reaction between the phenol and thechloroether proceeds smoothly and in good yields. No catalyst isnecessary. In general, it is advisable to use an excess of the lowerboiling component, so that the temperature may be controlled morereadily. The mixture is refluxed, preferably under reduced pressure,from one to five hours. The reaction mixture can then be fractionatedWithout washing, or if extreme purity is desired, unreacted phenol canbe removed by washing with dilute aqueous alkali before distilling. Mostof these materials are colorless to yellow, almost odorless liquids.

The chemicals of the present invention may be applied to 1001 to beprotected against insects in undiluted form, or as dusts when admixedwith or adsorbed on powdered solid carriers, such as clay or talc, or asliquids or sprays when in a liquid carrier, as in solution in a suitablesolvent, or dispersed in a suitable non-solvent medium, for example,water. In protecting plants (the term including plant parts) which aresubject to attack by insects, the mixed aliphatic-aromatic acetals o1butyl chloral of the present invention are preferably applied as aqueousemulsions containing a dispersing agent. The chemicals may be usedadmixed with carriers that are active of themselves, for example, otherinsecticides, fungicides or bactericides. The mixed aliphaticaromaticacetals of butyl chloral may also be used as intermediates in organicsynthesis, and as high-boiling solvents.

The aliphatic 1,2,2,3-tetrachloro-n-butyl ethers used in the preparationof the mixed aliphaticaromatic acetals of butyl chloral may be preparedas described in another application of the present inventors Serial No.725,162, filed January 29, 1947, by adding the selected aliphaticalcohol to butyl chloral to form, quantitatively, the butyl chloralalcoholate and then converting the same by means of a halogenatingagent, such as phosphorus pentachloride, to the aliphatic1,2,2,8-tetrachloro-n-butyl ether with liberation of hydrogen chloride.The conversion of the alcoholate to the aliphatic1,2,2,3-tetrachloro-nbutyl ether is conveniently carried out in an inertsolvent, such as an ethyl ether, at room temperature or lower. Thereaction of ethyl alcohol with butyl chloral followed by thechlorination with phosphorus pentachloride to give theethyl-1,2,2,3-tetrachloro-n-butyl ether is shown in the reactionnumbered I below. The reaction of the ethyl 1,2,2,3-tetrachloro-n-butylether with phenol to give the mixed ethyl-phenyl acetalof butyl chloral(l-ethoxy-1-phenoxy-2,2,3-trichloro-n-butane) is shown in the reactionnumbered II below.

C./2.5 mm. was obtained. Refractive index, n 1.5050. Analysis calculatedas CsHgOCls, 64.60% Cl; found 64.69% Cl.

O-GzHs CH OHClOChOHO 0,1150}; omonolo ohofi l OH OO]H5 OH CHOlC ClzOHHC1+ Pooh 11 EXAMPLE IV 2 fi 5 Be'nyl 1,2,2,3-tetrachloro-n-butyl etherCHSOHGIC (31105 O I This compound was prepared from butyl chloral 01 g44 g.) using ether as a solvent, as described in 2 Example I. A yield of43 g. of colorless oil boiling oniaonoloolzog H01 l at 145-150 C./3 mm.was obtained. Refractive 0 index, n 1.5426. Analysis calculated asDetailed procedures for the preparation of various aliphatic1,2,2,3-tetrachloro n buty1 ethers from which may be prepared the mixedaliphatic-aromatic acetals of butyl chloral of the present invention aredescribed in Examples I to VI below.

EXAMPLE I Ethyl 1,2,2,3detrachloyo-n-butfl ether.

One gram mole (46 g.) of anhydrous ethyl alcohol was added slowly withthorough agitation to -1 mole (175.5 g.) of butyl chloral. The solutionwarmed rapidly as the alcohol was added. The clear colorless alcoholatewas allowed to cool, then dissolved in 100 cc. of dry ethyl ether. Thissolution was added slowly, with stirring and cooling in an ice waterbath, to 210 g. of phosphorus pentachloride in 100 cc. of dry ethylether. The solution was added at such a rate that the temperature of thereaction mixture did not climb much above 20 C. As soon as addition wascomplete, the cooling bath was removedfand stirring was continued foranother hour. Th ether solution I was poured into two or three volumesof ice water and was stirred vigorousl for one hour. The oil layer wasseparated and washed with dilute aqueous alkali until the wash watergave a slightly basic reaction and "finally with water. The ether wasremoved on the steam bath and the product was distilled rapidly underreduced pressure. A yield or 180 g. of water white liquid boiling at 3486 C./4 mm. was obtained. Refractive index, n 1.4869. Analysiscalculated for CsHioOCh, 59.12% Cl; found 58.87% Cl.

EXAMPLE II Isobatyl 12,2,3-tetrachZOro-n-butyl ether EXAMPLE IIIfi-chloroethyl 1,2,2,3-tetrachZoro-n-butyl ether This compound wasprepared from anhydrous ethylene chlorohydrin (20 g.), butyl chloral (44g.) and phosphorus pentachloride (54 g.) using ether as a solvent as inExample I. A yield of 44 g. Of almost water white liquid boiling at80-108 C11H12GC14, 46.96% 01; found 47.23% (:1.

EXAMPLE v Allyl 1,2,2,3-tetrachloro-n-butyl ether This compound wasprepared from allyl alcohol (14.5 g.), butyl chloral (44 g.) andphosphorus pentachloride (50 g.) using other as a solvent, as describ din Example I. A ield of 33 g. of a water White oil boiling at 78-81 C./2.5 mm. was obtained. Refractive index, n 1.4958. Analysis calculatedas CvHmOClr, 56.29% Cl; found- 5'6.85% Cl.

EXAMPLE VI Cycloh-exyl 1,2,2,3-tetrwchZoro=n -butyl ether This compoundwas prepared from cyclohexanol (25 g.) butyl chloral (44 g.) andphosphorus pentachloride (55 g.) using other as a solvent, as describedin Example I. A yield of 35 s. of a water white oil boiling at 118-121"C./2. 2 fri'm. was obtained. Refractive index, 'n 1.5061. Analysiscalculated as CmI-ImOCh, 48.23% Cl; found 48.37% Cl.

A wide variety of aliphatic alcohols may be employed to giv the desired.aliphatic 1,2,2,3-tetrachloro-n-butyl ether. Examples of aliphaticradicals in the aliphatic eth'ei' linkage are 'alliyl (e. g'., methyl,ethyl, n-propyl, isopropyl, n-b'utyl, sec. butyl, 'n-arnyl, isoarnyl,h'eptyl, octyl, do'decyl) cycloalkyl '(e. g., cyclohexyl), 'aralkyl (e.g., benzyl), alkenyl (e. g, allyl, 'm'e'thallyl) and substituted alkylgroups, suchfa-s h'aloalkyl, cyanoalkyl, alkoxyalkyl, hydroxyalkyl andaryloxyalkyl (e. g., fi chloroethyl, fi-cyanoethyl, 'y-chloropropyl,fi+p-chlorophenoxy=-ethyl). Thus, further compounds illustrative of theinvention are:

,d-cyanoethyl 1,2,23-tetrachloro-n-butyl ether B-thiocyanoethyl1,'2,2,3-tetrachlbro-n-butyl ether fl-p-chlcrophenoxy-ethyl 1,2,2}tetracIuoro-nbutyletlier.

Detailed procedures for the preparation of various mixedaliphatic-aromatic acetals of butyl choral of the present invention fromvarious aliphatic 1,2,2,3-tetrachloro-n-butyl ethers prepared as shownin Examples 1 to VI, are described in Examples VII to XIV.

1 -etho:r:y-1 -phen'ory-2,2,3-triehloro-n-biztcme A solution of 28 gramsof ethyl 1,2;2,3-tetrachloro-n-butyl ether and 9.4 grams of phenol wasrefluxed under reduced pressure mm.) for 5 hours. The pressure wasreduced to 1 mm. of

mercury and the reaction mixture was fractionated. A yield of 12.6 g. ofa yellow oily liquid which boiled at 110-120 C./1 mm. was obtained.Refractive index, 71. 1.5221. Analysis calculated for C12H1502C13,35.74% C1; found 35.70% C1.

EXAMPLE VIII 1 -etho:cy-1- (p-chlorophenomy) -2,2,3-

trichloro-n-butane EXANIPLE IX 1 -ethoxy-1 (ZA-dichlorophenomy) -2,2,3-

trichloro-n-butane A solution of 35 g. of ethyl1,2,2,3-tetrachloron-butyl ether and 16.4 g. of 2,4-dichlorophenol wasrefluxed seventy-five minutes under about 100 mm. pressure. The reactionmixture was fractionated under reduced pressure, yielding '23 g. of apale yellow oil which boiled at 163-164 C./2 mm. Refractive index,1.5415. Analysis calculated for C12H13O2Cl5, 48.37% Cl; found 47.6% C1.

EXAMPLE X 1 -ethoa:y-1 (2,4,5-trz'chlorophenomy) -2,2,3-

trichZoro-n-butane A solution of 28 g. of ethyl1,2,2,3-tetrachloron-butyl ether and 19.7 g. of 2,4,5-trichlorophenolwas refluxed for five hours under about 100 mm. pressure. The reactionmixture was fractionated under reduced pressure, yielding 21 g. of ayellow viscous oil which boiled at 155-165 (1/1 mm. Refractive index, n1.5512. Analysis calculated for C12H1202C16, 53.06% Cl; found 52.90% Cl.

EXAMPLE XI 1 -fi-chZoroethoxy-1 -p-chZorophenoxy-2,2,3-

trichloro -n-buta'n.e

A solution of 10 g. of ,B-chloroethyl 1,2,23- tetrachloro-n-butyl etherand 10 g. of p-chlorophenol was heated for four and one-half hours underabout 100 mm. pressure. The reaction mixture was fractionated underreduced pressure, yielding 10.5 g. of light yellow oil which boiled at160-172 C./1.9 mm. Refractive index, n 1.5438. Analysis calculated forC12H13O2Cl5, 48.37% C1; found 47.32% 01.

EXAMPLE XII 1-isobutoccy-1-p-chlorophenowy-2,2,3-

trichZoro-n-butane A solution of 10 g. each of isobutoxy 1,2,2,3-tetrachloro-n-butyl ether and p-chlorophenol was refluxed under apressure of about 100 mm. for five hours. Fractionation of the reactionmixture yielded 12 g. of almost water white oil which boiled at 159-164C./2.2 mm. Refractive index, n 1.5227. Analysis calculated forC14H1802C14, 39.39% 01; found 39.0% C1.

1-aZlyZ0azu-1-p-chlorophen0xy-2,2,3-

trichZoro-n-butane A solution of 10 g. each of allyl 1,2,2,3-tetra-.

chloro-n-butyl ether and p-chlorophenol was re- EXAMPLE XIV 1cyclohexyloxy 1 p-chlorophenozry-2,2,3-trichloro-n-butane A solution of10 g. each of cyclohexyl 1,2,23- tetrachloro-n-butyl ether andp-chlorophenol was refluxed under a pressure of approximately mm. forthree and one-half hours. Fractionation of the reaction mixture yielded3.3 g. of a viscous yellow oil which boiled at -170 C./l mm.

Examples of other aliphatic groups in the alkyl ether linkage in thegeneral formula for the mixed aliphatic-aromatic acetals of butylchloral are: methyl, n-propyl, isopropyl, isobutyl, sec.- butyl, n-amyl,iso-amyl, 2-inethyl butyl, n-heptyl, n-dodecyl, ,B-hydroxyethyl,[-l-ethoXy-ethyl, 8- bromo-ethyl, a-chloropropyl, fi-cyano-ethyl.Examples of other aromatic groups in the aryl ether linkage in thegeneral formula are pentachlorophenyl, 2,4,6-trichloropheny1, p-tolyl,p-anisyl, p-fluorophenyl, p-nitrophenyl. Thus, further compoundsillustrative of the present invention are:

l-p-chloro-ethoxy-1-p-,chlorophenoxy-2,2,3 trichloro-n-butanel-fi-cyano-ethoxy-l-p-chlorophenoxy 2,2,3 trichloro-n-butanel-cyclohexyloxy-l- (p-tert-butyl phenoxy) -2,2,3-

trichloro-n-butane l-methoxy-1-p-fluorophenoxy-2,2,3 trichloro-nbutanel-ethoxy-l-(p-tolyloxy)-2,2,3-trichloro n butanel-ethoxy-l-(p-methoxy-phenoxy) 2,2,3-trichloro-n-butanel-ethoxy-l-(p-nitrophenoxy) 2,2,3-trichloro-nbutane l-ethoxy-l-(p-naphthoxy) 2,2,3-trichloro-n-butane.

The following examples illustrate the effectiveness of various mixedaliphatic-aromatic acetals of butyl chloral as insecticides:

EXAMPLE A Pinto bean leaves were sprayed with 1% aqueous emulsions ofvariou aliphatic mixed aliphatic-aromatic acetals of butyl chloral, theemulsions containing small amounts of commercial dispersing agents(Emulfor EL which is a reaction product of alkylene oxide and 'castoroil, and Nacconal which is an alkyl aryl sulfonate) which were known tobe non-toxic to the organisms under test. The bean leaves were theninfested with approximately 40 Mexican bean beetles (Epilctchnaoarioestis) in four replicates of each treatment. The bean leaves wereplaced in separate covered petri dishes. After 48 hours observationsdisclosed mortalities of the beetles on the leaves treated with thevarious mixed aliphatic-aromatic acetals of butyl chloral, as shown inthe following table. In untreated leaves there was no mortality of thebeetles.

EXAMPLE B Leaves of the broad bean (Vicia. faba) infested with peaaphids (M am'osiphum pisi) were sprayed with 1% aqueous emulsions ofvarious mixed aliphatic aromatic acetais of butyl chloral, the emuL-sions containing small amounts of Emulfor EL and Nacconal NR which wereknown to be nontoxic to the organisms under test. There were a variablenumber of insects in four replicates of each treatment. Observationswere made after 24 hours to disclose the kill of aphids. The per centmortality and the number of pea aphids on the leaves treated with thevarious mixed aliphatic-aromatic acetals of butyl chloral are shown int1 e following table. In the untreated (check) leaves infested with 192aphids, the mortality was 1.8%.

- N0. of Per cent 0116mm Aphids Mortality l-Ethoxy-l-phenoxy-Q,2,3-trichloro-n-butane 139 87. 1 l-Ethoxy-l-(p-chlorophenoxy)-2,2,S-trichloro n-butanc 184 92. 4 1 Ethoxy-l (2,4-dichlorophenoxy) 2,3-tr'- ch1oro-n-butane 156 94. 9 LEthoxy-l-(2,4,5-trichlorophenoxy chloro-n-b utanc 205 63. 9l-B-chloroothoxy-l- (p-chlorophenoxy) -2, 2,3-

trichloron-butane 216 58. 8 l -Isobutoxy 1 (p chlorophenoxy) -2,2,3-tr1- chloro-n-butane 194 S0. 9 1 Allyloxy 1 (p chlorophenoxy) 2,2,3-tr1- chloro-n-butane 170 62. 4 l-Cyclohexyloxy-l- (p -chlorophcnoxy)-2, ,3-

trichloro-n-butane 155 73.

EXAMPLE C Pinto bean leaves infested with red spider mites (Tetranychustelarz'us) were sprayed with 1% aqueous emulsions of various mixedaliphatic-aromatic acetals of butyl chloral, the emulsions containingsmall amounts of Emulior EL and Nacconal NR. which were known to benon-toxic to the organisms under test. There were variable numbers ofmites in four replicates of each treatment. Observations were made after24 hours to disclose the kill of mites. The percent mortality and numberof mites on the leaves 8 treated with the various mixedaliphatic-aromatic acetals of butyl chloral are shown in the tablebelow. In untreated (check) leaves intested with 210 red spider mites,the mortality wa 3.4% after 24 hours.

- No. of Percent Chemlcal Mites Mortality l-Ethoxy-l-phenoxy-2,2,3-trichlorobutane. 124 99. 2 l-Ethoxy-l-(p-chlorophenoxy)-2,2,3-trich1orcn-butane 98. 5 1-Ethoxy-1-(24- dichlorophenoxy) 2,2,3tri chloro-n-butane 212 100. 0 l-Etlioxy-l- (2,4,5-trichlorophenoxy)-2,2,3-trichlorobutanc 1- 164 86.0 l-fi-chloroethoxy-l-(p-chlorophenoxy) 2, 2,3

trichloro-n-butane 187 85. 0 l-Iscbutoxy-l-(p chlorophenoxy) 2,2,3 trichloro-n-butane 143 98. 6 l-Oyclohexyloxy-l-(p-chlorophenoxy) 2,2,3

trichloro-n-butane 323 93. 8

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. A 1 alkoxy-1-aryl0Xy-2,2,3-trichloro-n-butane.

2. An insecticidal composition comprising 1-alkoxy-1-phenoXy-2,2,3-trichl0ro-n-butane.

3. A 1-alkoxy-l-chlorophenoxy-2,2,3-trichloron-butane.

4. A l-ethoxy-1-aryloxy-Z,2,3-trich1oro-n-butane.

5. 1 ethoxy 1-phenoxy-2,2,3-trichloro-n-butane.

6. A 1-ethoxy-1-chloropl1en0xy-2,2,3-triohl0ron-butane.

'7. l ethoxy l-(p chlorophenoxy) -2,2,3-trichloro-n-butane.

8. l-ethoxy-l-(2,4-dichlorophenoxy) -2,2,3-tr ichloro-n-butane.

9. An insecticidal composition comprising a 1- alkoxy1-phenoXy-2,2,3-trichloro-n-butane and a powdered solid carriertherefor.

10. An insecticidal composition comprising a 1 alkoxy 1phenoxy-2,2,3-trichloro-n-butane, said aqueous emulsion containing adispersing agent.

WALTER D. HARRIS. THEODORE W. KERR.

REFERENQES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,129,025 Rieche et al. Sept. 6,1938 2,299,911 Bruson et al July 30, 1940 2,314,304 Britton Mar. 16,1943 2,327,338 Carswell Aug. 24, 1943 2,415,263 MacMullen Feb. 18, 19472,425,534 Hester et a1 Aug. 12, 1947 OTHER REFERENCES Beilstein, vol. 1,page 665.

1. A 1 - ALKOXY-1-ARYLOXY-2,2,3-TRICHLORO-N-BUTANE.